Process and catalyst for the polymerization and copolymerization of olefins

ABSTRACT

A method of polymerizing and copolymerizing olefins with a novel catalyst comprising (a) the reaction product of an inorganic compound of a polyvalent metal having a valence of at least three, e.g., TiC14, and a solid, bivalent metal hydroxylated inorganic phosphate, e.g., Ca5(PO4)3OH, or hydroxychloride, e.g., Mg(OH)C1, (b) a metal, a hydride, or an organometallic compound of metals of Groups IVB , VB and VIB, e.g., Sn(C4H9)4, and (c) a Group IIIB or VB halide, e.g., A1C13.

United States Patent [72] Inventors Felix Bloyaert [56] References Cited::"B R;";;' es J UNITED STATES PATENTS 11 re u ruxe acques 3,214,4[7l/l965 Bloyaert etal 260/88.2 L 3,400,] 10 9/l968 Dassesse et al.260/882 [21] Appl. No. 430,207 221 Filed Feb. 3, 1965 FOREIGN PATENTSPatented Nov. 30, 197] 1,306,453 9/1962 France [73] Assignee Solvay &Cie 860,407 2/l962 Great Britain g5 Prlomy 1964 Primary Examiner-JosephL. Schofer :31:3 Assistant Examiner- Edward J. Smith E H. L b' t Theportion of he term of the patent Attorneys Robert E Burns and mmanue o ao subsequent to Sept. 3, 1985, has been m dischimed- ABSTRACT: A methodof polymerizing and copolymerizing olefins with a novel catalystcomprising (a) the reaction product of an inorganic compound of apolyvalent metal hav- [54] PROCESS AND CATALYST FOR THE ing a valence'of at least three, e.g., TiC 1,, and a solid, bivalent POLYMERIZATIONAND COPOLYMERIZATION metal hydroxylated inorganic phosphate. e g., CaPOQ OH. :EP' or hydroxychloride, e.g., Mg(OH)Cl, (b) a metal, a hydride,mmsNo Drawings or an organometallic compound of metals of Groups lVB[52] [1.8. CI zoo/88.2, VB and WE. -g-. Sn( 4H )4. n a Group lllB VB252/429 C, 252/430, 260/93], 260/949 E lide, e.g., A 1C 1,. [51 Int. ClC08! 1/56,

C08f 3/06 Field of Search 260/949 D,

PROCESS AND CATALYST FOR THE POLYMERIZATION AND COPOLYMERIZATION OFOLEFTNS The present invention relates to a process for thepolymerization and copolymerization ofolefins in the presence of novelsolid catalysts. In another aspect it relates to solid catalysts forolefin polymerization.

it is know to polymerize and copolymerize olefins in the presence of aternary catalyst consisting of (a) a metal, a hydride, or anorganometallic compound of metals 'of Groups lVB, VB, and W8 of theperiodic table, (General Chemistry, Markham and Smith Houghton MifflinCo., New York, New York, 1954, page US '(b) a 'mineral compound of apolyvalent metal having a valence of at least three, and (c) a halide ofan element of Group [H8 or Group VB(Belgian patent 547,618

It is also known to polymerize olefins in the presence of supportedbinary catalysts. In particular, in the Belgian patent 552,550, it hasbeen proposed to polymerize ethylene in the presence of a catalystconsisting of an organometallic coinpound and a derivative of atransition metal, deposited on an inert support such as silicon carbide,calcium phosphate, or magnesium or sodium carbonate.

French Pat. l,29l,788 shows the polymerization of olefins in thepresence of a salt of a metal of Groups lll, IV, V or Vlll of theperiodic table, deposited on a support consisting of an inorganicchloride with rhombohedral structure, containing no atom of oxygen. Thiscatalyst is used with an organometallic cocatalyst.

In both processes discussed above and in a series of others of the sametype, a binary catalyst based on titanium halide and alkylaminum isdeposited on an inert support.

There has been perfected a series of catalysts associated with supportswhich are characterized by the fact that a compound of a transitionmetal is chemically bound to a hydoxylated support. The novel chemicalcombination obtained by the reaction of the compound of a transitionmetal with the hydroxyl groups of the support is then activated by anorganometallic compound and preferably by an alkylalurninum.

Catalysts of this type have particular properties which depend on thenature of the support.

Such a catalyst is described particularly in the French patentl,306,453. This catalyst is prepared by the reaction of anorganometallic compound with a combination of a transition metal whichis associated chemically with a hydroxylated inorganic phosphate.

Up to the present the polymerization of olefins in the presence of aternary catalyst as defined above, deposited or associated with asupport, has not been described.

It has now been discovered that, by chemically associating a ternarycatalyst of the type defined above with hydroxylated supports, catalystsare obtained which have unexpected and particularly importantproperties.

The process according to the present invention consists of carrying outthe polymerization or copolymerization of 'olefins in the presence of acatalyst which forms on mixing: (a) the product of the reaction betweenan inorganic compound of a polyvalent metal having a valence of atleastthree and a solid support chosen from the group includinghydroxylated inorganic phosphates and hydroxychlorides of bivalentmetals, (b) a metal, a hydride, or an organometallic compound of metalsof Groups lVB, VB, and W8 of the periodic table, and (c)'a halide ofanelement ofGroup "IE or VB.

It is an object of this invention to provide an improved catalyst forthe polymerization of olefins.

Another object is to provide a method of polymerizing and copolymerizingolefins such as ethylene and propylene.

Still another object is to provide an olefin polymerization processutilizing a supported catalyst having improved activity.

Various other objects, advantages and features of this invention will beapparent to those skilled in the art from the following discussion.

It has in fact been discovered that among the supports containinghydroxyl groups usable for the preparation of the novel catalysts, twoparticular types, the hydroxylated phosphates and the hydroxychloridesof bivalent metals, are distinguished by their aptitude for leading tohighly active catalysts.

On the other hand, other solid hydroxylated compounds such as the silicaaluminas lead to catalysts which are not very active, and some of themfinally give completely inactive catalysts: This is the case with lime.

in the first group of supports, the hydroxylated phosphates, it has beenobserved that the calcium hydroxyapatite, with formula Ca. P0,);0H, isparticularly interesting. This product can be obtained by reactionbetween calcium nitrate and diammonium phosphate, or better still, fromlime and phosphoric acid. This support is then activated by heating at atemperature of 200 to 1000 C.

Examples of other hydroxylated phosphates of bivalent metals areBeryllium hydroxyphosphate, magnesium hydroxyphosphate, bariumhydroxyphosphate, zinc hydroxyphosphate, mercury hydroxyphosphate, andthe like.

Another type of supports giving highly active catalysts consists ofhydroxychlorides of bivalent metals M, corresponding to the formula M(OH)Cl. Preferably hydroxychlorides having a lamellar structure with thickpiling up of the anions are used. Magnesium hydroxychloride especiallycorresponds to this condition and can be used advantageously.

Examples of other hydroxylated chlorides of bivalent metals are:beryllium hydroxychloride, strontium hydroxychloride, cadmiumhydroxychloride, and the like.

These hydroxychlorides can be prepared according to conventional method,for example, from chlorides and oxides or hydroxides of bivalent metals.After reduction into particle fines and forceful drying, they can beused for the reaction with inorganic compounds of polyvalent metals.

The chemical fixation of the inorganic compounds of polyvalent metals isdone by DH groups. if M represents a polyvalent metal and X a monovalentreactive group fixed on M, the reaction with a hydroxylated supportradicals OH can be represented as follows: X,,M'+Z--0H-- Z-0MX,,-, +Xl-lExamples of inorganic compounds of polyvalent metals having a valence ofat least three that can be used for the preparation of the novelcatalysts of the invention are those compounds that are hydrocarbonsoluble and contain radicals that are reactive with hydroxyl groups;such compounds are selected, for example, from the halides andoxyhalides of the metals of Groups lll, IV, V, V! and Vlll. Examples ofcompounds that can be used are titanium tetrachloride, vanadiumtetrachloride, vanadium pentachloride, vanadyl trichloride, vanadyltribromide, chroniyl chloride, chromium hexachloride, ferric chloride,aluminum iodide, and the like.

The fixation reaction of the inorganic compound of a polyvalent metal isaccompanied by the liberation of decomposition products. When thiscompound is a chloride, a liberation of hydrogen chloride is observed,for example: TiCl ,+Z OH-- Cl Ti-OZ +HC1 These decompositions productsas well as the excess starting products are eliminated by washing thecatalyst.

The fixation reaction must be carried out protected from moisture, forexample by bringing to boiling a suspension of the hydroxylated compoundin a hydrocarbon such as hexane, xylene, or tetralin, where theinorganic compound of a polyvalent metal is dissolved. Generally anincrease in the amount of the polyvalent metal compound fixed on thesupport is observed when the reaction temperatures is raised.

As soon as the reaction is finished, the polyvalent metal compound isfixed chemically to the support; it cannot be eliminated therefrom byphysical means such as washing.

The support-polyvalent metal compound combination thus obtainedconstitutes the first constituent of a novel ternary pounds of metals ofGroups lVB, VB, and W8 of h i di Fifteen hundred mg. of impregnatedsupport obtained as table, is preferably a tetraalkyltin, for exampletetrabutyltin. above is introduced into a l.5-liter autoclave ofstainless steel, Examples of metals, hydrides, or organometalliccompounds with l0.7 ml. of a solution in hexane containing 200 g./literof of the metals of Groups lVB, VB, and WE are: tin, lead, a mixture ofSn(C,H,,)4 and AlCl in a molar ratio Sn(C,H,,)

silane, phosphine, arsine, tellurium hydride, tetrabutyltin, 5 4/AlCl of1:1.

TABLE Nmnhnr ol groups pm" 1,000 carbon atoms it u i w v t" It on on. 0cm um 'lypvv of catalyst llSlll [or II Il It I liulgluu pnlmil M71518.

tetracyclohexylantimony, tetrabenzyllead, tetraphenylger- Thetemperature of the autoclave is brought to 80 C. and

manium, tetra(methylcyclopentyl)bismuth, tetrapropyltin, the ethylenepressure to 2 l 3 .s.i.a. After two hours of reach il d, d h lik Thorganic di l of h tion, the autoclave is vented and 30 g. ofpolyethylene whose ganometallic compound can be alkyl, cycloalkyl, arylor comi y i 62 g./cm. is withdrawn.

binations thereof, such as alkaryl, aralkyl, alkcycloalkyl, and Theresults of the analysis of this polyethylene by infrared the like,andcan contain up to eight carbon atoms. spectrometry are given thefollowing table, where they are The third constituent of the catalyst,which must be chosen compared with those characterizing a polyethyleneobtained from the halides of the Group "18 and VB elements, is adincontact with a ternary catalyst which is not chemically asvantageouslychosen among the halides of aluminum, particuciated with a support.

larly the chloride. EXAMPLE [1 Examples of halides of the elements ofGroups [118 and VB are: boron chloride, aluminum chloride, galliumiodide, indium fluoride, thallium bromide, phosphorus trichloride,antimony trichloride, bismuth trichloride, arsenic fluoride, arsenouschloride, and the like.

The process according to the invention is applied to the polymerizationand copolymerization olefms, preferably hav- The autoclave Y by a 9 drypropylene Then 9.3 ml. ofa solution in hexane containing 4l0 g./liter ofmg two to eight carbons atoms, and especially to the manufac- SMQHBBOand 126 g lmer of MCIl (molar ratio sn/M turehofbpolyetilglene z i POMS-].25) is introduced the rein. Then 355 g. of propylene is met utent- 0-met entento octeneand cbpolymers of :th;lene-pro plene and eth5lee-butenbl 40 condessed ig g the-mperature of the a IS The use of ternarycatalysts chemically bound to a support P q t to at temperature gaseousm y T' associates the advantages of the ternary catalysts with those ofls i zgg l Ki lf f f fi fig g zgzrg q va ue o p.s.|.a. equi 1 n m, e eco- 2335; 22:3311?5 :23:? zf z g igggshg ggsggfig sition of the liquidmixture of monomers IS 70 mol percent propylene and 30 percent ethylene.

Into a 1.5-liter stainless steel autoclave 1255 mg. of calciumhydroxylapatite of the formula Ca -,(P0,),Ol-l, activated by heating at300 C. for 24 hours, on which 15.8 mg. of Ti has been chemically fixedby reaction with TiCl, in solution in hexane, is introduced.

Showmg the excepuonal Propemes ba manufactured After lbur hours ofreaction, the autoclave is vented and 73 Thus, the polyethylene preparedwith the novel catalysts acg. of a rubbery ethylene propyienecopoiymeicontaining cordlng to the invention contains less than one Cl-lgroup per about 20 mol percent of propylene is withdrawn f the thousandcarbon atoms, shows no vinylidene double needs, toclava ltsimrinsicviscosityis 35 and Shows 'y low cohiems of double bohds and Shows Aswill be apparent to those skilled in the art, various other y low comemsof Vinyl double bonds and Internal modifications can be made in thisinvention without departing (bonds). Its true density is very high andexceeds 0.962 f the Spirit or Scope th fl g-/cm.. We claim:

Used for the copolymeflzafioh of ethylene and Propylene l. A catalystwhich forms on mixing components comprislhese hovel catalysis allow,from a reaction mixture of give" 5 5 ing (a) the reaction product oftitanium tetrachloride, with a composition, copolymers to be obtainedwhich are richer in id support hi h i magnesium h d hl ride, (b) P pythan those mahufacml'ed with the know" catalysts- Sn(R) R being alkyl,cycloalkyl, aryl or combinations thereof The following examples withoubeing imitative, are containing up to eight carbon atoms, and (c) ahalide of alutended to illustrate the present invention. minum 2 2. Acatalyst according to claim 1, in which said component (c) is aluminumchloride.

EXAMPLE 3. A polymerization process which comprises a contacting underpolymerization conditions at least one olefin having two Twenty Slams gz- 6H20l5 heated at iha Vehfi' to eight carbon atoms with catalyst whichforms on mixing lated oven. The molten and dehydrated mass thus obtainedis components comprising th ti r d t f tit i ground, then brought to 285C. in a quartz tube in a current hl id i h a lid support hi h imagnesium of y nitrogen Thus magnesium hydroxychloride, hydroxychloride,(b) Sn(R), R being alkyl, cycloalkyl, aryl or Mg(0H)Cl,is obtained.combinations thereof containing up to eight carbon atoms,

This product is immediately reacted with TiCl, by heating to d a h lid fl i boiling in a solution TiCl, in xylene. After reaction, the titani-4, A polymerization process according to claim 3, in which um chemicallyfixed on the support is determined and there is said component (c) isaluminum chloride. found 13.7 mg. Ti/g. ofsupport.

2. A catalyst according to claim 1, in which said component (c) isaluminum chloride.
 3. A polymerization process which comprisescontacting under polymerization conditions at least one olefin havingtwo to eight carbon atoms with catalyst which forms on mixing componentscomprising (a) the reaction product of titanium tetrachloride, with asolid support which is magnesium hydroxychloride, (b) Sn(R)4 R beingalkyl, cycloalkyl, aryl or combinations thereof containing up to 8carbon atoms, and (c) a halide of aluminum.
 4. A polymerization processaccording to claim 3, in which said component (c) is aluminum chloride.